Abstract
The adsorption of organoactinide complexes on dehydroxylated alumina (DA) yields coordinatively unsaturated, highly active catalysts for several demanding chemical transformations. Thus, in the case of Th(η 3-allyl) 4 supported on dehydroxylated γ-alumina (DA), facile arene hydrogenation and alkane activation processes can be effected in slurry reactions at 90°C and P H 2 = 30–180 psi. Benzene reduction occurs at a turnover frequency of ≈ 25000 h −1 per active site and cyclohexane CH exchange with D 2 at ≈ 1300 h −1 per active site. Active site characterization using D 2O poisoning, hydrogenolysis, and CH 3Cl dosing indicates ⩽ 8 ± 1 % of the Th surface sites are catalytically significant. EPR and XPS spectroscopy provide no evidence for Th oxidation states less than +4. The mechanisms for the above processes are discussed in terms of electrophilic “four-center” activation processes in which the active sites appear to bear sterically significant, nonhydridic ancillary ligation.
Published Version
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